US3561925A - Production of ammonia and sulfur from ammonium sulfites or sulfides - Google Patents

Production of ammonia and sulfur from ammonium sulfites or sulfides Download PDF

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Publication number
US3561925A
US3561925A US738471A US3561925DA US3561925A US 3561925 A US3561925 A US 3561925A US 738471 A US738471 A US 738471A US 3561925D A US3561925D A US 3561925DA US 3561925 A US3561925 A US 3561925A
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Prior art keywords
sulfur
ammonia
ammonium
sulfide
sulfides
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US738471A
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English (en)
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Andre Deschamps
Philippe Renault
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/026—Preparation of ammonia from inorganic compounds
    • C01C1/028—Preparation of ammonia from inorganic compounds from ammonium sulfate or sulfite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores

Definitions

  • ammonia must be regenerated from the thus obtained solu tions of ammonium sulfides or sulfites and the sulfur compound must be recovered under a useful form.
  • the process of this invention has for object to regenerate ammonia and to convert the acidic constituent of the salt into elemental sulfur.
  • the ammonium sulfite or sulfide is reacted with a substantially stoichiometrical amount of, respectively, hydrogen sulfide or sulfur dioxide in Order that the following reactions may take place:
  • the stoichiometrical amount is thus 2 moles of hydrogen sulfide for 1 mole of ammonium sulfide in the case of reaction (I) and one mole of sulfur dioxide per 2 moles of ammonium sulfide, in the case of reaction (II).
  • the stoichiometrical amount is the same with acidic sulfides or sulfites.
  • the conversion of ammonium sulfide or sulfite to sulfur and ammonia is carried out in the presence of a liquid phase containing at least by Weight, and more preferably from 20 to 100%, of a compound chosen from the two following groups:
  • R and R same or different are hydrogen atoms, monovalent hydrocarbon radicals of 1-20 and preferably 1-5 carbon atoms, monovalent radicals of formula R CO where R is a monovalent hydrocarbon radical, such as alkyl of 1-20 and preferably 1-5 carbon atoms; R which may be same or dilferent, are bivalent hydrocarbon radicals of 2-10 and preferably 2-5 carbon atoms, advantageously linear or branched alkylene radicals; and n is an integer from 1 to 50, preferably 5 to 20.
  • Phosphoric esters of the general formula PO (0R where the R radicals which may be same or difierent, are monovalent hydrocarbon radicals containing 1-20 and preferably 3-10 carbon atoms, such as alkyl, cycloalkyl and aryl, or radicals of the formula 4 )m 5 where R, is a bivalent hydrocarbon rest of 2 or 3 carbon atoms, R is a hydrogen atom or a hydrocarbon rest of 1-5 carbon atoms and m is an integer of l, 2 or 3.
  • esters having a solubility in water'lower than 1% by weight at 20 C. and a dissolving power for water lower than 7% by weight at 20 C.
  • the liquid phase in the presence of which is preferably carried out the reaction may comprise water and optionally low amounts of additional solvents.
  • the conversion of ammonium sulfides or sulfites to sulfur and ammonia may be carried out at a temperature which, if the atmospheric pressure is used, will be at least C. and for example between and C. according to the nature of the liquid phase which is used as reaction phase. Usually C. will not be overpassed.
  • the reaction will be carried out at a temperature which will not be lower by more than 10 C. than the boiling point of water under the selected pressure.
  • the reaction temperature will be at least this boiling temperature at this same pressure.
  • Ammonium sulfite or sulfide may be used in the solid or liquid state, for example as a solution in water or in diluted aqueous ammonia.
  • the necessary additional gas, H S or S0 may be introduced pure or diluted in a gas such as nitrogen.
  • sulfite there is meant both the so-called sulfite and the bisulfite or a mixture of these.
  • sulfite there is meant both the so-called sulfite and the bisulfite or a mixture of these.
  • the same observation may be made with respect to the sulfide. It is then possible to treat according to this invention both the solutions of sulfide or bisulfide, or solutions containing a mixture of these, which is usually the case.
  • the salt (ammonium sulfite or sulfide) to be converted to sulfur and ammonia may be contacted with another salt (respectively ammonium sulfite or sulfide), one or the two salts introduced into the liquid phase defined herebelow being initially solid or dissolved in a solvent, for example water.
  • Any apparatus allowing contact between a gas and a liquid may be used to carry out the reaction, for example a column with plates or packing, the liquid phase being still or circulating.
  • the sulfide or sulfite for example in the form of an aqueous solution, is injected through pipe 1 at the bottom of a packed column which has been filled with solvent, for example a phosphoric ester.
  • solvent for example a phosphoric ester.
  • line 2 there is introduced at the bottom of this column a substantially stoichiometrical amount of S or 8H, according to the nature of the treated solutionzarnmonium sulfite or sulfide.
  • an 20 ammonium sulfite or sulfide may be injected, for example in the form of an aqueous solution, through pipe 2.
  • the formed sulfur separates; it is withdrawn from the lower part of the column through pipe 3. Ammonia and water resulting from the reaction escape as vapor through line 4 from the top of the column.
  • one of the reactants for example S0 is in excess it will be withdrawn from the top of the column together with ammonia and steam. It will be advantageously recycled, for example as ammonium sulfite, after cooling of the gaseous efiluent from the column.
  • EXAMPLE 1 From the bottom of a packed column containing 500 ccm. of tri(2-butoxy ethyl) phosphate maintained at 106 C. there is injected at a rate of 100 ccm. per hour an aqueous solution of neutral ammonium sul'fite (NH S0 at a concentration of 2 moles per liter. H 5 is introduced at the bottom of the column at a rate of 9 liters per hour, together with nitrogen (90 liters per hour).
  • NH S0 neutral ammonium sul'fite
  • the conversion rate of the sulfite is 90% and may be easily increased by varying the operating conditions such as, for example, the dimensions of the packed column, its efficacy, the rate of the feed solution and the like. Sulfur is recovered in the crystalline form at the basis of the apparatus. No by-product could be detected such as sulfate or thiosulfate.
  • Example 1 is repeated, operating at 120 C. with an injection rate of 150 cm. per hour of a 2 moles per liter aqueous solution of ammonium bisulfide. S0 is introduced from the bottom of the column at a rate of 3.4 liters per hour, diluted in nitrogen (30 liters per hour).
  • Sulfur is recovered in the liquid state from the basis of the column.
  • the conversion rate is 100% and the yield of sulfur is quantitative since no by-product may be detected.
  • Example 2 is repeated, however replacing tri(2-butoxy ethyl) phosphate by 500 cm. of polyethyleneglycol of molecular weight about 400. All other conditions remaining unchanged, the same results as in Example 2 are obtained.
  • Example 2 is repeated, however replacing the solvent by 500 cm. of triisobutyl phosphate. Substantially same results as in Example 2 are obtained.
  • a liquid phase containing at least 10% by weight of a compound selected from the group consisting of higher alcohols, polyols, monoand polyalkylene glycols, esters and ethers of the alcohols, polyols and glycols and phosphoric esters of the general formula PO( OR) wherein R is an alkyl, cycloalkyl or aryl monovalent hydrocarbon radical containing 1 to carbon atoms, or a radical of the formula -(R O) R in which R, is a hydrocarbon radical containing 2 to 3 carbon atoms, R is a hydrogen atom or a hydrocarbon radical containing 1 to 5 carbon atoms and m is a number from 1 to 3, and recovering sulfur therefrom as well as water and ammonia in the gaseous state.
  • R is an alkyl, cycloalkyl or aryl monovalent hydrocarbon radical containing 1 to carbon atoms, or a radical of the formula -(R O) R in which R, is a hydrocarbon radical containing 2
  • the monoand polyalkylene glycols are of the general formula R O(R -O) R wherein R and R are selected from the group consisting of hydrogen, a monovalent hydrocarbon radical containing 1 to 20' carbon atoms and a monovalent radical of the formula RCO wherein R is a monovalent hydrocarbon radical containing 1 to 20 carbon atoms, R is a bivalent hydrocarbon radical containing 2 to 10 carbon atoms and n is a number from 3.
  • R is a monovalent hydrocarbon radical containing 1 to 20 carbon atoms
  • R is a bivalent hydrocarbon radical containing 2 to 10 carbon atoms
  • n is a number from 3.
  • ammonium sulfite and ammonium sulfide are used as an aqueous solution.
  • ammonium sulfide or ammonium sulfite is obtained from washing a gas containing, respectively, hydrogen sulfide or sulfur dioxide with an aqueous solution of ammonia.
  • ammonia and sulfur is manufactured from ammonium bisulfite or ammonium bisulfide.
  • liquid phase is selected from the group consisting of tri(2-butoxy ethyl) prosphate, polyethylene glycol and triisobutyl phosphate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Industrial Gases (AREA)
US738471A 1967-06-26 1968-06-20 Production of ammonia and sulfur from ammonium sulfites or sulfides Expired - Lifetime US3561925A (en)

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FR111962 1967-06-26

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US (1) US3561925A (enrdf_load_stackoverflow)
JP (1) JPS4828560B1 (enrdf_load_stackoverflow)
BE (1) BE717088A (enrdf_load_stackoverflow)
DE (1) DE1767828C3 (enrdf_load_stackoverflow)
ES (1) ES355423A1 (enrdf_load_stackoverflow)
FR (1) FR1568748A (enrdf_load_stackoverflow)
GB (1) GB1221844A (enrdf_load_stackoverflow)
NL (1) NL6808970A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846538A (en) * 1971-09-27 1974-11-05 Inst Francais Du Petrole Process for regenerating strong bases from solutions of their sulfides and simultaneously producing sulfur
US3882222A (en) * 1971-03-09 1975-05-06 Inst Francais Du Petrole Process for purifying a gas containing oxygenated sulfur compounds and recovering sulfur using ammonia liquors
US3962410A (en) * 1972-11-20 1976-06-08 Institut Francais Du Petrole, Des Carburants Et Lubrifiants Process for purifying industrial gases containing hydrogen sulfide with sulfur production
US3966891A (en) * 1972-10-20 1976-06-29 Institut Francaise Du Petrole, Des Carburants Et Lubrifiants Process for manufacturing sulfur from a solution of sodium sulfite
US4039649A (en) * 1974-08-14 1977-08-02 Institut Francais Du Petrole Process for removing sulfur from waste waters containing sulfuric acid
US4058591A (en) * 1974-09-05 1977-11-15 Institut Francais Du Petrole Process for purifying waste water containing ammonium sulfate
US4174383A (en) * 1973-12-17 1979-11-13 Institut Francais Du Petrole Process for purifying a sulfur dioxide containing gas with production of elemental sulfur

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882222A (en) * 1971-03-09 1975-05-06 Inst Francais Du Petrole Process for purifying a gas containing oxygenated sulfur compounds and recovering sulfur using ammonia liquors
US3846538A (en) * 1971-09-27 1974-11-05 Inst Francais Du Petrole Process for regenerating strong bases from solutions of their sulfides and simultaneously producing sulfur
US3966891A (en) * 1972-10-20 1976-06-29 Institut Francaise Du Petrole, Des Carburants Et Lubrifiants Process for manufacturing sulfur from a solution of sodium sulfite
US3962410A (en) * 1972-11-20 1976-06-08 Institut Francais Du Petrole, Des Carburants Et Lubrifiants Process for purifying industrial gases containing hydrogen sulfide with sulfur production
US4174383A (en) * 1973-12-17 1979-11-13 Institut Francais Du Petrole Process for purifying a sulfur dioxide containing gas with production of elemental sulfur
US4039649A (en) * 1974-08-14 1977-08-02 Institut Francais Du Petrole Process for removing sulfur from waste waters containing sulfuric acid
US4058591A (en) * 1974-09-05 1977-11-15 Institut Francais Du Petrole Process for purifying waste water containing ammonium sulfate

Also Published As

Publication number Publication date
DE1767828A1 (de) 1971-09-30
ES355423A1 (es) 1970-03-01
DE1767828C3 (de) 1980-03-27
JPS4828560B1 (enrdf_load_stackoverflow) 1973-09-03
DE1767828B2 (de) 1979-07-26
GB1221844A (en) 1971-02-10
BE717088A (enrdf_load_stackoverflow) 1968-12-02
FR1568748A (enrdf_load_stackoverflow) 1969-05-30
NL6808970A (enrdf_load_stackoverflow) 1968-12-27

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